US12477942B2

US12477942B2 - Organic metal compound and application thereof

Info

Publication number: US12477942B2
Application number: US17/297,999
Authority: US
Inventors: Liangliang YAN; Lei Dai; Lifei Cai
Original assignee: Guangdong Aglaia Optoelectronic Materials Co Ltd
Current assignee: Guangdong Aglaia Optoelectronic Materials Co Ltd
Priority date: 2018-12-27
Filing date: 2019-11-02
Publication date: 2025-11-18
Also published as: CN111377969A; JP7179252B2; WO2020134570A1; KR102671242B1; CN111377969B; DE112019005183T5; DE112019005183B4; JP2022509647A; US20220115603A1; KR20210068531A

Abstract

The present invention relates to an organic metal compound and application thereof. The organometallic compound has a structure as shown in Formula I. The compound provided by the present invention has the advantages of low sublimation temperature, high light and electricity stability, high luminous efficiency, long lifetime, high color saturation and the like, can be used in an organic light-emitting device, and particularly has a possibility of being applied to an AMOLED industry as a red luminescent phosphorescent material.

Description

TECHNICAL FIELD

The present invention relates to the technical field of organic electroluminescence, in particular to an organic light-emitting material suitable for an organic electroluminescence device, and particularly relates to an organic metal compound and application thereof to the organic light-emitting device.

BACKGROUND

At present, an organic electroluminescence device (OLED) as a new generation of display technology has gained more and more attention in aspects of display and lighting technologies, and has very broad application prospects. However, the performance, such as luminous efficiency, driving voltage and lifetime, of an OLED device still needs to be further enhanced and improved in comparison to market application requirements.

Generally, according to a basic structure of the OLED device, various organic functional material thin films with different functions are sandwiched between metal electrodes, like a sandwich structure. Holes and electrons are respectively injected from a cathode and an anode under the driving effect of current. After the holes and the electrons move for a certain distance, they are recombined in a light-emitting layer, and are released in a form of light or heat, thereby generating light emission of the OLED. However, an organic functional material is a core composition of the organic electroluminescence device, and the thermal stability, photochemical stability, electrochemical stability, quantum yield, film forming stability, crystallinity, color saturation and the like of the material are all main factors influencing the performance of the device.

Generally, the organic functional material includes a fluorescent material and a phosphorescent material. The fluorescent material is generally an organic small molecular material and can only emit light by using 25% singlet states, so that the luminous efficiency is very low. Due to a spin orbit coupling effect caused by heavy atom effects, besides the use of 25% singlet states, the phosphorescent material can also use energy of excitons of 75% triplet states, so that the luminous efficiency can be improved. However, compared with a fluorescent material, the phosphorescent material starts later, and needs to be improved in aspects of thermal stability, lifetime, color saturation and the like of the material, and this is a challenging subject. Various organometallic compounds have been developed as phosphorescent materials at present. For example, the invention patent document CN107973823 discloses a class of quinoline iridium compounds, but the color saturation and the device performance, especially the luminous efficiency and the lifetime of the device of the compounds need to be improved; and the invention patent document CN106459114 discloses a class of iridium compounds coordinated by a β-diketone ligand, but the compounds a have high sublimation temperature and a poor color saturation, particularly, the device performance is not ideal, and further improvement is needed.

SUMMARY

One objective of the present invention is to provide a phosphorescent compound which has the advantages of low sublimation temperature, high light and electrochemical stability, high color saturation, high luminous efficiency, long lifetime of a device and the like, can be used in an organic electroluminescence device, and can be particularly used as a red light emitting dopant to be applied to OLED industry.

An organometallic compound has a structural formula as shown in Formula I:

- wherein one in A1 to A4 is a C—C bond connected with a ring E, one is a C-M bond connected with metal M, one is CR₄, and another is CR₀or N; one in A5 to A8 is CR₃, and the other three are independently represented as CR₀or N; wherein M is a metal with the atomic weight greater than 40;
- R₀to R₄are independently selected from hydrogen, deuterium, halogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C6 to C30 aralkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, an amino group, a substituted or unsubstituted C1 to C10 silyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C8 heteroaryl group, a cyano group, nitrile, isonitrile or a phosphino group, wherein the substitution refers to substitution by deuterium, F, Cl, Br, a C1 to C4 alkyl group, a C1 to C4 alkoxy group, a C3 to C6 cycloalkyl group, an amino group substituted by a C1 to C4 alkyl group, a cyano group, nitrile, isonitrile, or a phosphino group, and at least one of R₃and R₄is not hydrogen;
- Z is independently selected from O, S, Se, C (R) 2, Si(R) 2, NR, BR or POR, wherein R is independently selected from a substituted or unsubstituted C1 to C10 alkyl group or alkoxy group, a substituted or unsubstituted C2 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C18 heteroaryl group; and
- wherein X—Y is a monoanionic bidentate ligand, wherein the sum of a and b equals to a valence state of the metal M.
- Preferably, X—Y is a OO type and CN type ligand; and M is one of metals in Os, Ir, Pt, Pd, Ru, Rh or Au.

A preferable compound has a structure as shown in the following Formula II:

- wherein n is a positive integer of 1 to 2, A is CR₀or N, wherein R₀to R₄are independently selected from hydrogen, deuterium, a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C1 to C8 heteroalkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C8 aralkyl group, a substituted or unsubstituted C1 to C8 silyl group, or a C1 to C8 aryl group or heteroaryl group unsubstituted or substituted by a C1 to C4 alkyl group; and at least one of R₃and R₄is not hydrogen.

As a preferable compound, A is CH.

As a preferable compound, A is N.

As a preferable compound, an R3 substituent group is located adjacent to N.

As a preferable compound, R3 is D or an alkyl group containing at most 4 carbon atoms, particularly preferably an alkyl group at least containing one D, more particularly preferably CD3.

As a preferable compound, Z is O, S, NR or C(R)₂, wherein R is independently selected from a substituted or unsubstituted C1 to C8 alkyl group.

As a preferable compound, an R₄substituent group is located adjacent to a metal-carbon bond.

As a preferable compound, an R₄substituent group is located opposite to a metal-carbon bond.

As a preferable compound, X—Y is different from a left ligand.

As a preferable compound, X—Y is a 1,3-dione compound.

A preferable compound is the following compound:

Preferably, Z is O, R₁to R₄are independently selected from hydrogen, deuterium, a substituted or unsubstituted C1 to C4 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C8 aralkyl group, or a C1 to C8 aryl group or heteroaryl group unsubstituted or substituted by a C1 to C4 alkyl group; wherein at least one of R₃and R₄is not hydrogen.

R₁to R₄are independently selected from hydrogen, deuterium, a substituted or unsubstituted C1 to C4 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a C1 to C4 alkyl group substituted by a phenyl group, or a phenyl group substituted by a C1 to C4 alkyl group; wherein at least one of R₃and R₄is not hydrogen.

A preferable compound is the following compound:

One objective of the present invention is further to provide an OLED phosphorescent material containing the above compound.

One objective of the present invention is further to provide an OLED device containing the above compound.

The material of the present invention has the advantages of low sublimation temperature, high light and electrochemical stability, high color saturation, high luminous efficiency, long lifetime of a device and the like. The material of the present invention used as a phosphorescent material can convert a triplet excited state into light, so that the luminous efficiency of the organic electroluminescence device can be improved, and the energy consumption is reduced.

DETAILED DESCRIPTION OF THE EMBODIMENTS

The following embodiments are merely for the convenience of understanding the technical invention and should not be construed as specifically limiting the present invention.

Raw materials, solvents and the like used in the compound synthesis of the present invention were purchased from suppliers known to those skilled in the art, such as Alfa and Acros.

Embodiment 1

Synthesis of Common Intermediates:

Synthesis of Compound 2:

Compound 1 (27.2 g, 0.12 mol, 1.2 eq), 1-chloroisoquinoline (16.3 g, 0.1 mol, 1.0 eq) and Cs₂CO₃(97.5 g, 0.3 mol, 3.0 eq) and Pd(dppf)Cl₂(3.655 g, 0.05 mol, 0.05 eq) were put into a flask. 1 L of anhydrous toluene was added. Under the protection effect of N₂, stirring back flow was performed at 110° C. for 16 h. Cooling was performed to reach a room temperature, and concentration was performed to remove an organic solvent. 1 L of dichloromethane and 1 L of water were added into residues, and stirring delamination was performed. An organic phase was sequentially washed by H₂O (500 ml*3) and a saturated sodium chloride aqueous solution (500 ml*3). After drying by sodium sulphate, filtration was performed. An organic solvent was removed from filter liquor through concentration. Off white solids were obtained. The solids were purified through mashing by EtOH, and Compound 2 (24.33 g, yield: 78.7%) was obtained. Mass spectrum: 310.12 (M+H), 1HNMR: 8.42 (d, 1H), 7.92 (dd, 1H), 7.87 (dd, 1H), 7.71 (dd, 1H), 7.50-7.57 (m, 3H), 7.30 (dd, 1H), 6.99-7.20 (m, 4H), 2.35 (S,3H).

Synthesis of Compound 3:

Compound 2 (18.5 g, 0.06 mol, 3.0 eq) and IrCl₃3H₂O (7.04 g, 0.02 mol, 1.0 eq) were put into a flask. 2-ethoxyethanol (133.4 ml) and deionized water (66.7 ml) were added. A mixed solution was subjected to stirring back flow at 110° C. for 16 h under the protection effect of N₂. After the cooling to a room temperature, filtration was performed. Filter residues were sequentially dried by methanol (100 ml*3) and n-hexane (100 ml*3) to obtain Compound 3 (9.38 g, 55.4%). The obtained compound was directly used for a next step without purification.

Synthesis of CPD 1:

Compound 3 (5.08 g, 3 mmol, 1.0 eq) was dissolved in ethylene glycol monoethyl ether (30 ml). Anhydrous sodium carbonate (6.36 g, 60 mmol, 20.0 eq) and acetylacetone (3 g, 30 mmol, 10.0 eq) were sequentially added. After the addition was completed, under the protection effect of N₂, a mixed solution was stirred for 16 h at 40° C., and was cooled to the room temperature. 2 g of diatomite and 300 ml of dichloromethane were added into reaction liquid. Then, the mixed solution was filtered through diatomite and silica gel. The dichloromethane was removed from the obtained filter liquid in a spinning manner. Additionally, 40 ml of isopropanol was added into a residual solution. Red solids were separated out. Filtration was performed. The solids were subjected to pulping treatment through ethyl acetate to obtain a target compound CPD 1 (2.56 g, 46.8%). 2.56 g of CPD 1 crude products were sublimated and purified to obtain sublimated pure CPD 1 (2 g, 78.1%). Mass spectrum: 909.23 (M+H)

Synthesis of CPD 3:

Compound 3 (5.08 g, 3 mmol, 1.0 eq) was dissolved in ethylene glycol monoethyl ether (30 ml). Anhydrous sodium carbonate (6.36 g, 60 mmol, 20.0 eq) and 3,7-diethyl-4,6-nonanedione (6.36 g, 30 mmol, 10.0 eq) were sequentially added. After the addition was completed, under the protection effect of N₂, a mixed solution was stirred for 16 h at 40° C., and was cooled to the room temperature. 2 g of diatomite and 300 ml of dichloromethane were added into reaction liquid. Then, the mixed solution was filtered through diatomite and silica gel. The dichloromethane was removed from the obtained filter liquid in a spinning manner. Additionally, 40 ml of isopropanol was added into a residual solution. Red solids were separated out. Filtration was performed. The solids were subjected to pulping treatment through ethyl acetate to obtain a target compound CPD 3 (2.69 g, 43.9%). 2.69 g of CPD 3 crude products were sublimated and purified to obtain sublimated pure CPD 3 (1.78 g, 66.2%). Mass spectrum: 1021.36 (M+H)

Embodiment 2

Synthesis of Common Intermediates:

Synthesis of Compound 5:

Compound 4 (28.92 g, 0.12 mol, 1.2 eq), 1-chloro-6 isopropylisoquinoline (20.5 g, 0.1 mol, 1.0 eq) and Cs₂CO₃(97.5 g, 0.3 mol, 3.0 eq) and Pd(dppf) Cl₂(3.655 g, 0.05 mol, 0.05 eq) were put into a flask. 1 L of anhydrous toluene was added. Under the protection effect of N₂, stirring back flow was performed at 110° C. for 16 h. Cooling was performed to reach a room temperature, and concentration was performed to remove an organic solvent. 1 L of dichloromethane and 1 L of water were added into residues, and stirring delamination was performed. An organic phase was sequentially washed by H₂O (500 ml*3) and a saturated sodium chloride aqueous solution (500 ml*3). After drying by sodium sulphate, filtration was performed. An organic solvent was removed from filter liquor through concentration. Off white solids were obtained. The solids were subjected to column chromatography purification by ethyl acetate/petroleum ether. Compound 5 (28.12 g, yield: 76.8%) was obtained. Mass spectrum: 367.18 (M+H), 1HNMR: 8.4 (d,1H),7.81 (dd, 1H), 7.74 (dd, 1H), 7.71 (s, 1H), 7.50 (s, 1H), 7.27-7.36 (m, 3H), 7.1 (d,1H),3.12 (q,1H),2.55 (s, 3H), 2.35 (s, 3H), 1.29 (d, 6H).

Synthesis of Compound 6:

Compound 5 (22 g, 0.06 mol, 3.0 eq) and IrCl₃3H₂O (7.04 g, 0.02 mol, 1.0 eq) were put into a flask. 2-ethoxyethanol (133.4 ml) and deionized water (66.7 ml) were added. A mixed solution was subjected to stirring back flow at 110° C. for 16 h under the protection effect of N₂. After the cooling to a room temperature, filtration was performed. Filter residues were sequentially dried by methanol (100 ml*3) and n-hexane (100 ml*3) to obtain Compound 6 (9.86 g, 51.3%). The obtained compound was directly used for a next step without purification.

Synthesis of CPD 13:

Compound 6 (5.76 g, 3 mmol, 1.0 eq) was dissolved in ethylene glycol monoethyl ether (30 ml). Anhydrous sodium carbonate (6.36 g, 60 mmol, 20.0 eq) and acetylacetone (3 g, 30 mmol, 10.0 eq) were sequentially added. After the addition was completed, under the protection effect of N₂, a mixed solution was stirred for 16 h at 40° C., and was cooled to the room temperature. 2 g of diatomite and 300 ml of dichloromethane were added into reaction liquid. Then, the mixed solution was filtered through diatomite and silica gel. The dichloromethane was removed from the obtained filter liquid in a spinning manner. Additionally, 40 ml of isopropanol was added into a residual solution. Red solids were separated out. Filtration was performed. The solids were subjected to pulping treatment through ethyl acetate to obtain a target compound CPD 13 (2.33 g, 38%). 2.33 g of CPD 13 crude products were sublimated and purified to obtain sublimated pure CPD 13 (1.72 g, 73.8%). Mass spectrum: 1023.34 (M+H)

Synthesis of CPD 16:

Compound 6 (5.76 g, 3 mmol, 1.0 eq) was dissolved in ethylene glycol monoethyl ether (30 ml). Anhydrous sodium carbonate (6.36 g, 60 mmol, 20.0 eq) and 2,8-dimethyl-4,6-nonanedione (6.36 g, 30 mmol, 10.0 eq) were sequentially added. After the addition was completed, under the protection effect of N₂, a mixed solution was stirred for 16 h at 40° C., and was cooled to the room temperature. 2 g of diatomite and 300 ml of dichloromethane were added into reaction liquid. Then, the mixed solution was filtered through diatomite and silica gel. The dichloromethane was removed from the obtained filter liquid in a spinning manner. Additionally, 40 ml of isopropanol was added into a residual solution. Red solids were separated out. Filtration was performed. The solids were subjected to pulping treatment through ethyl acetate to obtain a target compound CPD 16 (2.12 g, 32%). 2.12 g of CPD 16 crude products were sublimated and purified to obtain sublimated pure CPD 16 (1.65 g, 77.8%). Mass spectrum: 1107.43 (M+H)

Synthesis of CPD 17:

Compound 6 (5.76 g, 3 mmol, 1.0 eq) was dissolved in ethylene glycol monoethyl ether (30 ml). Anhydrous sodium carbonate (6.36 g, 60 mmol, 20.0 eq) and 2-acetylphenol (4.08 g, 30 mmol, 10.0 eq) were sequentially added. After the addition was completed, under the protection effect of N₂, a mixed solution was stirred for 16 h at 40° C., and was cooled to the room temperature. 2 g of diatomite and 300 ml of dichloromethane were added into reaction liquid. Then, the mixed solution was filtered through diatomite and silica gel. The dichloromethane was removed from the obtained filter liquid in a spinning manner. Additionally, 40 ml of isopropanol was added into a residual solution. Red solids were separated out. Filtration was performed. The solids were subjected to column chromatography separation to obtain a target compound CPD 17 (2.58 g, 41%). 2.58 g of CPD 17 crude products were sublimated and purified to obtain sublimated pure CPD 17 (1.88 g, 73.1%). Mass spectrum: 1059.34 (M+H)

Synthesis of CPD 18:

Synthesis of Compound 7:

Compound 6 (19.2 g, 0.01 mol, 1.0 eq) was dissolved in DCM (500 ml). Silver trifluoromethanesulfonate (5.25 g, 0.02 mol, 2.0 eq) and methanol (50 mmol) were sequentially added into reaction liquid. After the addition was completed, under the protection effect of N₂, a mixed solution was stirred for 16 h at 30° C. Insoluble solids were removed from reaction liquid through silica gel and diatomite. The filter liquid dried in a spinning manner. Compound 7 (22 g) was obtained. The obtained product was directly used for a next step of reaction.

Synthesis of CPD 18:

Compound 7 (3.41 g, 3 mmol, 1.0 eq) and 2-phenylpyridine (1.4 g, 9 mmol, 3.0 eq) were dissolved in absolute ethanol (100 ml). After the addition was completed, under the protection effect of N₂, a mixed solution was subjected to back flow stirring for 16 h at 80° C., and was cooled to the room temperature. Filtration was performed. Filter residues were washed for 3 times sequentially by methanol and n-hexane. Drying was performed to obtain a target compound CPD 18 (1.68 g, 52%). 1.68 g of CPD 18 crude products were sublimated and purified to obtain sublimated pure CPD 18 (1.24 g, 73.8%). Mass spectrum: 1078.36 (M+H)

Synthesis of CPD 24:

Compound CPD 18 (2.15 g, 2 mmol, 1.0 eq) and Ethanol-d6 (100 ml) were dissolved in anhydrous THF (50 ml). After the addition was completed, under the protection effect of N₂, a mixed solution was subjected to back flow stirring for 16 h at 80° C., and was cooled to the room temperature. Filtration was performed. Filter residues were washed for 3 times sequentially by methanol and n-hexane. Drying was performed to obtain a target compound CPD 24 (2.15 g, 99%). 2.15 g of CPD 24 crude products were sublimated and purified to obtain sublimated pure CPD 24 (1.54 g, 71.6%). Mass spectrum: 1078.36 (M+H)

Synthesis of CPD 19:

A synthesis method was the same as that of CPD 24, and a target compound CPD 19 (1.88 g, 99%) was obtained. 1.88 g of CPD 19 crude products were sublimated and purified to obtain sublimated pure CPD 19 (1.42 g, 75.5%). Mass spectrum: 1028.38 (M+H)

Synthesis of CPD 22:

A synthesis method was the same as that of CPD 24, and a target compound CPD 22 (2.35 g, 99%) was obtained. 2.35 g of CPD 22 crude products were sublimated and purified to obtain sublimated pure CPD 22 (1.64 g, 69.9%). Mass spectrum: 1113.47 (M+H)

Synthesis of CPD 23:

A synthesis method was the same as that of CPD 24, and a target compound CPD 23 (2.52 g, 99%) was obtained. 2.52 g of CPD 23 crude products were sublimated and purified to obtain sublimated pure CPD 23 (1.92 g, 76.2%). Mass spectrum: 1065.38 (M+H)

Embodiment 3

Synthesis of CPD 79:

Synthesis of Compound 9:

Compound 8 (29.1 g, 0.12 mol, 1.2 eq), 1-chloroisoquinoline (16.3 g, 0.1 mol, 1.0 eq) and Cs₂CO₃(97.5 g, 0.3 mol, 3.0 eq) and Pd(dppf)Cl₂(3.655 g, 0.05 mol, 0.05 eq) were put into a flask. 1 L of anhydrous toluene was added. Under the protection effect of N₂, stirring back flow was performed at 110° C. for 16 h. Cooling was performed to reach a room temperature, and concentration was performed to remove an organic solvent. 1 L of dichloromethane and 1 L of water were added into residues, and stirring delamination was performed. An organic phase was sequentially washed by H₂O (500 ml*3) and a saturated sodium chloride aqueous solution (500 ml*3). After drying by sodium sulphate, filtration was performed. An organic solvent was removed from filter liquor through concentration. Off white solids were obtained. The solids were separated through column chromatography, and Compound 9 (23.41 g, yield: 72.1%) was obtained. Mass spectrum: 326.1 (M+H), 1HNMR: 8.51 (d, 1H), 7.71-7.82 (m, 5H), 7.50-7.60 (m, 3H), 7.30-7.4 (m, 2H), 7.10 (d, 1H), 2.21 (s, 3H).

Synthesis of Compound 10:

Compound 9 (19.5 g, 0.06 mol, 3.0 eq) and IrCl₃3H₂O (7.04 g, 0.02 mol, 1.0 eq) were put into a flask. 2-ethoxyethanol (133.4 ml) and deionized water (66.7 ml) were added. A mixed solution was subjected to stirring back flow at 110° C. for 16 h under the protection effect of N₂. After the cooling to a room temperature, filtration was performed. Filter residues were sequentially dried by methanol (100 ml*3) and n-hexane (100 ml*3) to obtain Compound 3 (8.54 g, 48.6%). The obtained compound was directly used for a next step without purification.

Synthesis of CPD 79:

Synthesis and purification methods were the same as those of CPD 1, and a target compound CPD 79 (3.26 g, 46.8%) was obtained. 3.26 g of CPD 79 crude products were sublimated and purified to obtain sublimated pure CPD 79 (2.33 g, 71.6%). Mass spectrum: 941.18 (M+H)

Embodiment 4

Synthesis of CPD 80:

Synthesis of Compound 12:

Compound 11 (30.3 g, 0.12 mol, 1.2 eq), 1-chloroisoquinoline (16.3 g, 0.1 mol, 1.0 eq) and Cs₂CO₃(97.5 g, 0.3 mol, 3.0 eq) and Pd(dppf)Cl₂(3.655 g, 0.05 mol, 0.05 eq) were put into a flask. 1 L of anhydrous toluene was added. Under the protection effect of N₂, stirring back flow was performed at 110° C. for 16 h. Cooling was performed to reach a room temperature, and concentration was performed to remove an organic solvent. 1 L of dichloromethane and 1 L of water were added into residues, and stirring delamination was performed. An organic phase was sequentially washed by H₂O (500 ml*3) and a saturated sodium chloride aqueous solution (500 ml*3). After drying by sodium sulphate, filtration was performed. An organic solvent was removed from filter liquor through concentration. Off white solids were obtained. The solids were separated through column chromatography, and Compound 12 (21.34 g, yield: 63.7%) was obtained. Mass spectrum: 336.17 (M+H), 1HNMR: 8.51 (d, 1H), 7.71-7.82 (m, 5H), 7.50-7.60 (m, 3H), 7.30-7.4 (m, 2H), 7.10 (d, 1H), 2.32 (s, 3H), 1.67 (s, 6H).

Synthesis of Compound 13:

Compound 12 (20.1 g, 0.06 mol, 3.0 eq) and IrCl₃3H₂O (7.04 g, 0.02 mol, 1.0 eq) were put into a flask. 2-ethoxyethanol (133.4 ml) and deionized water (66.7 ml) were added. A mixed solution was subjected to stirring back flow at 110° C. for 16 h under the protection effect of N₂. After the cooling to a room temperature, filtration was performed. Filter residues were sequentially dried by methanol (100 ml*3) and n-hexane (100 ml*3) to obtain Compound 13 (8.96 g, 49.9%). The obtained compound was directly used for a next step without purification.

Synthesis of CPD 80:

Synthesis and purification methods were the same as those of CPD 1, and a target compound CPD 80 (3.54 g, 47.9%) was obtained. 3.54 g of CPD 80 crude products were sublimated and purified to obtain sublimated pure CPD 80 (2.45 g, 69.2%). Mass spectrum: 961.33 (M+H)

Corresponding materials were selected, and could be used for synthesis and sublimation by the same similar methods to obtain other compounds.

Application example: manufacture of organic electroluminescence device

A 50 mm*50 mm*1.0 mm glass substrate with an ITO (100 nm) transparent electrode was ultrasonically cleaned for 10 min in ethanol. After drying at 150° C., N₂Plasma treatment was performed for 30 min. The washed glass substrate was mounted on a substrate support of a vacuum evaporation device. Firstly, a compound HATCN was evaporated on the surface of one side with a transparent electrode wire in a mode of covering a transparent electrode to form a thin film with a thickness of 5 nm. Then, a layer of HTM1 was evaporated to form a thin film with a thickness of 60 nm. Next, a layer of HTM2 was evaporated on the HTM1 thin film to form a thin film with a thickness of 10 nm. Then, a host material CBP and a doping compound (comparative compound X, CPD X) were evaporated on the HTM2 thin film in a co-evaporation mode, a thickness of the film is 30 nm, and a proportion of the host material to the doping material was 90%: 10%. An AlQ3 film layer (25 nm) and an LiF film layer (1 nm) were sequentially evaporated on a light-emitting layer. Finally, a layer of metal A1 (100 nm) was evaporated to be used as an electrode.

Evaluation: The above devices were subjected to device performance test. In each embodiment and comparative example, a constant current power supply (Keithley 2400) was used, current with a constant current density flowed through a light-emitting element, and a spectroradiometry radiation luminance meter (CS 2000) was used for testing the light-emitting spectrum. At the same time, a voltage value was measured, and the time (LT90) that the test brightness was 90% of the initial brightness was measured. The results were as follows:


			Power	Peak
Doping	Starting	Current	efficiency	wavelength	LT90@
material	voltage V	efficiency Cd/A	lm/W	nm	3000 nits

Embodiment	CPD 1	4.21	24	17.90	614	162
1
Embodiment	CPD 3	4.12	28	21.34	615	178
2
Embodiment	CPD 13	4.05	31	24.03	620	211
3
Embodiment	CPD 16	3.99	33	25.97	626	232
4
Embodiment	CPD 17	3.97	30	23.73	623	235
5
Embodiment	CPD 18	3.96	32	25.37	622	264
6
Embodiment	CPD 19	3.88	32	25.90	622	268
7
Embodiment	CPD 22	3.86	34	27.66	628	312
8
Embodiment	CPD 23	3.79	32	26.51	625	295
9
Embodiment	CPD 24	3.82	31	25.48	624	281
10
Embodiment	CPD 79	3.98	26	20.51	616	168
11
Embodiment	CPD 80	4.11	28	21.39	615	176
12
Comparative	Comparative	4.56	21	14.46	610	102
example 1	compound 1
Comparative	Comparative	4.41	20	14.24	612	116
example 2	compound 2
Comparative	Comparative	4.64	21	14.21	611	94
example 3	compound 3
Comparative	Comparative	4.88	18	11.58	608	82
example 4	compound 4

Through comparison of data in the above table, it could be known that compared with that using comparative compounds, an organic electroluminescence device using the compound of the present invention as a dopant showed more excellent performance in aspects of driving voltage, luminous efficiency and device lifetime.

Comparison of sublimation temperature: the sublimation temperature is defined as the temperature corresponding to a vacuum degree of 10-7 Torr and an evaporation rate of 1 angstrom per second. The test results were as follows:


		Sublimation
	Doping material	temperature

	CPD 1	263
	CPD 3	262
	CPD 13	252
	CPD 16	258
	CPD 17	260
	CPD 18	262
	CPD 19	254
	CPD 22	259
	CPD 23	260
	CPD 24	261
	CPD 79	262
	CPD 80	261
	Comparative	280
	compound 1
	Comparative	288
	compound 2
	Comparative	286
	compound 3
	Comparative	276
	compound 4

Through comparison of data in the above table, it could be known that the compound of the present invention has a lower sublimation temperature, and is favorable for industrial application.

The above results show that the compound of the present invention has the advantages of low sublimation temperature, high light and electrochemical stability, high color saturation, high luminous efficiency, long lifetime of a device and the like, can be used in an organic electroluminescence device, and can be particularly used as a red light emitting dopant to realize the possibility of being applied to OLED industry.

Claims

The invention claimed is:

1. An organometallic compound, having a structural formula as shown in Formula I:

wherein:

one in A₁to A₄is a C—C bond connected with a ring E, one is a C-M bond connected with metal M, one is CR₄, and another is CR₀or N;

one in A₅to A₈is CR₃, and the other three are independently represented as CR₀or N;

M is a metal with the atomic weight greater than 40;

R₀to R₄are independently selected from hydrogen, deuterium, halogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C6 to C30 aralkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, an amino group, a substituted or unsubstituted C1 to C10 silyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C8 heteroaryl group, a cyano group, a isocyano group, or a phosphino group, wherein the substitution refers to substitution by deuterium, F, Cl, Br, a C1 to C4 alkyl group, a C1 to C4 alkoxy group, a C3 to C6 cycloalkyl group, an amino group substituted by a C1 to C4 alkyl group, a cyano group, a isocyano group or a phosphino group;

at least one of R₃and R₄is not hydrogen;

Z is independently selected from O, S, Se, C(R)₂, Si(R)₂, NR, BR or POR, wherein R is independently selected from a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C 30 aryl group, a substituted or unsubstituted C1 to C18 heteroaryl group; and

X-Y is a monoanionic bidentate ligand, wherein the sum of a and b equals to a valence state of the metal M.

2. The organometallic compound according to claim 1, wherein:

X-Y is a OO type and CN type ligand; and

M is one of metals in Os, Ir, Pt, Pd, Ru, Rh or Au.

3. The organometallic compound according to claim 2, having a structure as shown in Formula II:

wherein:

n is a positive integer of 1 to 2;

A is CR₀or N;

R₀to R₄are independently selected from hydrogen, deuterium, a substituted or unsubstituted C1 to C8 alkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C8 aralkyl group, a substituted or unsubstituted C3 to C10 silyl group, or a C6 to C8 aryl group or C1 to C8 heteroaryl group unsubstituted or substituted by a C1 to C4 alkyl group; and

at least one of R₃and R₄is not hydrogen.

4. The organometallic compound according to claim 3, wherein A is CH.

5. The organometallic compound according to claim 3, wherein A is N.

6. The organometallic compound according to claim 5, wherein an R₃substituent group is located adjacent to N.

7. The organometallic compound according to claim 5, wherein R₃is D or an alkyl group with at most 4 carbon atoms.

8. The organometallic compound according to claim 7, wherein R₃is an alkyl group at least containing one D.

9. The organometallic compound according to claim 8, wherein R₃is CD3.

10. The organometallic compound according to claim 3, wherein the position of R₄substituent group is a position adjacent to metal Ir—C bond.

11. The organometallic compound according to claim 3, wherein the position of R₄substituent group is a position opposite to metal Ir—C bond.

12. The organometallic compound according to claim 1, wherein:

Z is O, S, NR or C(R) 2, and

R is independently selected from a substituted or unsubstituted C1 to C8 alkyl group.

13. The organometallic compound according to claim 12, wherein X—Y is different from a left ligand.

14. The organometallic compound according to claim 13, wherein X—Y is a 1,3-dione compound.

15. An organic electroluminescence device, comprising the organometallic compound according to claim 1.

16. An organic electroluminescence device according to claim 15, comprising a light-emitting layer, the light-emitting layer comprising a doped material of a phosphorescent host material, wherein the doped material is the organometallic compound according to claim 1.

17. The organometallic compound according to claim 3, having one of the following compounds:

18. The organometallic compound according to claim 17, wherein:

Z is O, S or C(R)₂, R₁to R₄are independently selected from hydrogen, deuterium, a substituted or unsubstituted C1 to C4 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C8 aralkyl group, or a C6 to C8 aryl group or C6 to C8 heteroaryl group unsubstituted or substituted by a C1 to C4 alkyl group; and

at least one of R₃and R₄is not hydrogen.

19. The organometallic compound according to claim 18, wherein:

R₁to R₄are independently selected from hydrogen, deuterium, a substituted or unsubstituted C1 to C4 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a phenyl group substituted by a C1 to C4 alkyl group; and

at least one of R₃and R₄is not hydrogen.

20. The organometallic compound according to claim 19, having one of the following structural formulas: